Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides

Jensen, Mark P.; Chiarizia, R.; Ulicki, Joseph S.; Spindler, Brian D.; Murphy, Daniel J.; Hossain, M. Mahmun; Roca-Sabio, Adrián; Blas, Andrés de; Rodríguez‐Blas, Teresa

doi:10.1080/07366299.2015.1046292

Cited by 38 publications

(28 citation statements)

References 44 publications

(52 reference statements)

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“…The large ionic radius of 1.108(4) Å for eight‐coordinate Am III , and the availability of a large number of frontier orbitals (5f, 6p, 6d, 7s, and 7p) that could potentially be involved in bonding gives rise to rich coordination chemistry with americium. Careful design of ligands that target either the cation size or even specific geometries around the metal centers has led to the development of potentially viable complexants for Ln/Am, Am/Cm, and Ln/Cm separations …”

Section: Figurementioning

confidence: 83%

“…Carefuld esign of ligandst hat targete ither the cation size or even specific geometries aroundt he metal centers has led to the developmento fp otentially viable complexantsf or Ln/Am,A m/Cm,a nd Ln/Cm separations. [12][13][14][15] In this regard, it has been noted that p-back bonding occurs betweenasinglyo ccupied 5f orbitalf rom Am III and ap yridyl nitrogen atom in N-2-pyridylmethyl-diethylenetriamine-N,N',N'',N''-tetraacetic acid (DTTA-PyM)t hat is absenti nl anthanide complexes. [16] These studies augmentr ecent work by Adam et al that made use of a 15 N-labeled BTP derivative to probet he solution complexation of Am III .…”

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confidence: 99%

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Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Dan

Celis-Barros

White

et al. 2019

Chemistry A European J

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M(EtBTP) 3 ][BPh 4 ] 3 ·3CH 3 CN (M = Nd, Am;EtBTP = 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl 3 ·n H 2 Ow ith EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M 3 + cations bound by tridentate EtBTP ligands to create at ricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution,s ingle-crystal X-ray diffraction data also allowedr eductioni nb ond lengths esd's, such that as light contraction of D = 0.0158(18) in the AmÀNv ersus NdÀNb ond lengths waso bserved, even thought hese cationso stensibly have matchingi onic radii. Theoretical evaluation revealed enhanced metal-ligand bondingt hroughb ack donation in the [Am(EtBTP) 3 ] 3 + complex that is absentin[Nd(EtBTP) 3 ] 3 + .The importance of separating Am III from Ln III (Ln = lanthanide) cations stems from the need for more sensible ande fficient nuclear fuel cycles. The recycling of used nuclear fuel centers on the extraction of reusable uranium and plutonium through PUREX-like processes, and their re-use as mixed-oxide(MOX) nuclear fuels. [1] However,s toring the remaining waste after this extractioni sn on-trivial, because it is composed of fissionproducts, such as 90 Sr, 137 Cs, and lanthanides, as wella st he socalled minor actinides, neptunium, americium, and curium;t he latter actinides formed via neutron capture. After extraction of uranium and plutonium, the bulk of the waste consists of either stable isotopes or ones with relativelys hort half-lives, with notable long-lived exceptions that include 99 Tc (t1 = 2 = 2.11 10 5 years)a nd 135 Cs (t1 = 2 = 2.3 10 6 years).In contrast, americium is mostly presenti nt he form of 241 Am, which possesses an intermediate half-life of 432.2 years. Neutron capture and b decay processes primarily from the parenti sotope 241 Pu create > 1.3 kg of americium per ton of typical used nuclear fuel. [2] Thus, the term "minora ctinide" is inappropriate for americium and probably needs to be discard-ed in its entirety. Arguments can be made that it represents an energyr esourcef or fast neutron reactors, in which it can be fissioned, andt hat its removal from nuclear waste dramatically decreases the long-term radioactivity of ar epository.H owever, the primary driving force justifying its extraction is the heat load that it createsi nn uclear repository scenarios. Accordingly, separating americium from post-PUREX nuclear waste streams has becomeafocal point of radiochemicalinterest.Nitrogen-donor ligands, in contrastt ot raditional oxygen donors, such as phosphonates and organophosphates, have been the subjecto fi ncreased attention over the past several decades because of their potential use in f-block separations. These complexes possess the addedb enefito fi ncineration leadings olely to the formation of actinideo xides, thereby reducingt he volumeo fr adioactive waste in repositories. One particularly promising family of ligands that falls into this class are the tridentate, nit...

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Section: Figurementioning

confidence: 83%

mentioning

confidence: 99%

Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Dan

Celis-Barros

White

et al. 2019

Chemistry A European J

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show abstract

“…are available. In addition, acidic phosphorus compounds such as di-(2-ethylhexyl)phosphoric acid do not always exhibit the necessary properties to solve the problems on the selective separation of complex solution components [5][6][7], therefore the synthesis and study of extraction properties of new organic compounds is an urgent task [8][9][10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies

et al. 2021

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With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5–7, where the ArP(O)Ph2 group of phosphine oxide type is replaced by phosphonic fragments. Quantum-chemical modelling of the structures of phosphoryl-containing podands 1 and 5–7 has been performed, which was later confirmed by the data of X-ray diffraction. The features of extraction of nitric acid, as well as U(VI), Th(IV), Nd(III), and Ho(III) with compounds 1 and 5–7 from nitric acid media into 1,2-dichloroethane have been studied. The compositions of extracted complexes have been determined.

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“…[1][2][3] Their separation is usually performed in solution using solvent extraction technique (also called liquid-liquid extraction) which based on the transfer of metal species with lipophilic ligands (extractants) from an aqueous medium into an immiscible organic (solvent) phase. [4][5][6] To induce the selectivity and to improve the efficiency of solvent extraction, combination of different extractants could be employed to combine their coordination and solvating abilities vis-à-vis target metal ions. [7][8][9] There are numerous examples of synergic solvent extraction systems being used in the extraction of 4 f-block elements, particularly those involving phosphine oxides and trialkylphosphate extractants.…”

Section: Introductionmentioning

confidence: 99%

Solvent extraction of intra-lanthanides using a mixture of TBP and TODGA in ionic liquid

2020

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In this study, we have investigated the solvent extraction of yttrium(III) and lanthanide(III) ions from nitric acid solutions in an organic phase consisting of a mixture of two electrically neutral extractants, namely tri-n-butyl phosphate(TBP) and N,N,N',N'-tetra(n-octyl)diglycolamide (TODGA). We employed hydrophobic room-temperature ionic liquid 1-methyl-3-butyl-imidazolium bis(trifluoromethanesulfonyl)imide as more environmentally benign diluent as compared to conventional molecular solvents. The results revealed that the addition of TBP as a co-extractant to TODGA dissolved in this ionic liquid not only enhance greatly the metal ion extraction, but also induce high intra-lanthanide ion selectivity. This was attributed to the formation of complex lanthanide species with both organic extracting agents, TBP and TODGA. In addition, when IL is used as diluent, cationic exchange between metal-organic ligand species and IL cations and neutral complex extraction result in more efficient extraction. Moreover, hydrophobic anionic IL entities could be also involved in the extraction mechanism resulting in the lipophilic metal-organic ligand complexes. The synergic solvent combination of TODGA, TBP and ionic liquid offers a possibility of excellent separation among the lanthanide(III) ions.

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Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides

Cited by 38 publications

References 44 publications

Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies

Solvent extraction of intra-lanthanides using a mixture of TBP and TODGA in ionic liquid

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